Geometrical, electronic, and magnetic properties of the Sc-doped gold clusters, Au n Sc (n=1–8), have been studied using the density-functional theory within the generalized gradient approximation. An extensive structural search shows that the Sc atom in low-energy Au n Sc isomers tends to occupy the most highly coordinated position. The substitution of a Sc atom for an Au atom in the Au n+1 cluster markedly changes the structure of the host cluster. Moreover, we confirm that the ground-state Au 6 Sc cluster has a distortion to a lower D 2h symmetry. The relative stabilities and electronic properties of the lowest-energy Au n Sc clusters are analyzed based on the averaged binding energies, second-order energy differences, fragmentation energies, chemical hardnesses, and HOMO–LUMO gaps. It is found that the magic Au 3 Sc cluster can be perceived as a superatom with high chemical stability and its HOMO–LUMO gap is larger than that of the closed-shell Zr@Au 14 cluster. The high symmetry and spin multiplicity of the Au 3 Sc and Au 6 Sc clusters are responsible for their large vertical ionization potential and electron affinity. The magnetism calculations indicate that the magnetic moment of the Sc atom in the ground-state Au n Sc (n=2–8) clusters gradually decreases for even n and is completely quenched for odd n.